JP3854511B2 - Gel polymer electrolyte and electrochemical device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel-like polymer electrolyte simultaneously satisfying both of ion conductivity and mechanical strength and a secondary battery using it. <P>SOLUTION: In the gel-like polymer electrolyte comprising a matrix polymer (A) and a non-aqueous electrolytic solution (B), the gel-like polymer electrolyte in which (A) contains a polymer (A1) obtained by polymerizing an ethylenic unsaturated bond-containing polyol (a) represented by the following general formula (1): (HO)<SB>m</SB>R<SP>1</SP>(OX)<SB>r-m</SB>(1) [wherein R<SP>1</SP>is residual group of an r-valent polyol, X is an organic group having an ethylenic unsaturated bond, r is an integer of 3-10, m is an integer of 2-9 and r-m is an integer of 1-8], other polyol (b), an organic polyisocyanate (c) and if necessary, a monomer (d) having other ethylenic unsaturated bond is used. <P>COPYRIGHT: (C)2003,JPO

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel gel polymer electrolyte and its use. More specifically, the present invention relates to a gel polymer electrolyte having high ion conductivity and excellent mechanical strength, and an electrochemical element or electrochemical device using the gel polymer electrolyte.
[0002]
[Prior art]
Electrochemical devices such as aluminum electrolytic capacitors, electric double layer capacitors, and batteries are widely used in consumer electronic devices such as mobile phones and laptop computers. A conventional electrochemical element using an electrolyte solution has a problem in long-term reliability because liquid leakage tends to occur. In recent years, gel polymer electrolytes have been studied as electrolytes free from such problems.
In general, a gel polymer electrolyte has a structure in which an electrolytic solution in which an electrolyte salt such as a lithium salt is dissolved in a solvent is held in the polymer. Accordingly, in order to increase the mechanical strength, the proportion of the polymer may be increased, but the ionic conductivity is deteriorated as the proportion of the electrolytic solution decreases. On the contrary, if the amount of the electrolyte is increased, the ion conductivity is improved, but the mechanical strength is deteriorated. In the case of a battery using a gel polymer electrolyte, ionic conductivity is an important factor that directly affects battery performance, and mechanical strength is an important factor that directly affects the safety of the battery. Has been made.
[0003]
In recent years, gel polymer electrolytes using urethane (meth) acrylate polymers obtained by addition polymerization of (meth) acryloyl groups at the ends of polyurethane chains as gel polymer electrolytes with improved mechanical strength (for example, 8-295715 or JP-A-2001-35251) has been proposed.
[0004]
[Problems to be solved by the invention]
However, the gel polymer electrolyte does not have a sufficient crosslinking density and is not satisfactory in terms of mechanical strength.
The problem to be solved by the present invention is to provide a gel polymer electrolyte satisfying both ionic conductivity and mechanical strength at the same time, and an electrochemical device using the gel polymer electrolyte.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a gel polymer electrolyte comprising a matrix polymer (A) and a non-aqueous electrolyte (B), wherein (A) is an ethylenically unsaturated bond-containing polyol represented by the following general formula (1) It contains a polymer (A1) obtained by polymerizing (a), another polyol (b), an organic polyisocyanate (c), and, if necessary, another monomer (d) having an ethylenically unsaturated bond. A gel-like polymer electrolyte,
(HO) _m R ¹ (OX) _rm (1)
[Wherein R ¹ Is an residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, m is an integer of 2 to 9, and rm is an integer of 1 to 8. ]
And an electrochemical element, an electrochemical device, and a secondary battery using the same.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The ethylenically unsaturated bond-containing polyol compound (a) used in the present invention is a compound represented by the following general formula (1).
(HO) _m R ¹ (OX) _rm (1)
Where R ¹ Is an residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, m is an integer of 2 to 9, and rm is an integer of 1 to 8.
In the general formula (1), R ¹ Is a residue obtained by removing all OH groups from an r-valent polyol having a hydroxyl group equivalent of 30 to 200 and / or an alkylene oxide adduct of a condensate of phenol and formaldehyde (hereinafter abbreviated as novolak AOA).
From the viewpoint of the mechanical strength of the polymer electrolyte, R ¹ The hydroxyl equivalent is preferably 30 to 200.
A compound in which H is substituted for X instead of X from general formula (1), R ¹ (HO) _r Examples thereof include r-valent polyols and novolak AO adducts. Examples of the polyol include 3 to 10 valent polyhydric alcohols, alkylene oxide (hereinafter abbreviated as AO) adducts of the polyhydric alcohols, and AO adducts of polyhydric phenols (trivalent).
[0007]
Specific examples of the tri- to trivalent polyhydric alcohol include trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol and other alkanetriols; and alicyclic rings. Formula triols such as cyclohexanetriol, C 4-20 polyhydric alcohols (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like and their Intramolecular or intermolecular dehydrates; and sugars such as sucrose, glucose, mannose, lactose, methyl glucoside, and derivatives thereof).
Examples of AO adducts of polyhydric phenols (trivalent) include AO adducts of trivalent monocyclic phenols (such as pyrogallol and phloroglucin).
A novolac AOA includes a tri- to 10-valent novolac ethylene oxide adduct.
[0008]
Examples of the AO include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), α-olefin oxide. Styrene oxide, epichlorohydrin and the like, and combinations of two or more thereof. Among these, EO and / or EO and other AO [C3 or C4 alkylene oxides such as PO, 1,2-BO, 1,4-BO, etc., or two or more thereof. Hereinafter, it is abbreviated as other AO. ] Are preferred (random or block).
[0009]
In the general formula (1), X is a group having an ethylenically unsaturated bond. The number of unsaturated bonds is preferably 1 to 4, and more preferably 2. Examples of X include groups represented by the following general formulas (3) and (4).
-Q ₁ (3)
-COQ ₂ (4)
[Where Q ₁ Is an alkenyl group, alkadienyl group, alkatrienyl group or alkatetraenyl group having 2 to 24 carbon atoms, and Q ₂ Is Q ₁ Or it is the residue remove | excluding one COOH group from C4-C24 unsaturated polycarboxylic acid or its partial ester formation derivative. ]
[0010]
As a specific example of X, X = Q in the general formula (3) ₁ A linear, branched or cyclic alkenyl group having 2 to 24 carbon atoms, such as a vinyl group, an allyl group, an isopropenyl group, an oleyl group, or a cyclohexenyl group: a linear, branched or cyclic alkadienyl group having 2 to 24 carbon atoms A group such as a linole group; a linear, branched or cyclic alkatrienyl group having 2 to 24 carbon atoms, such as a linolenic group.
[0011]
Q in general formula (4) ₂ = Q ₁ In the case of X = COQ ₁ And an unsaturated acyl group having 3 to 25 carbon atoms, such as an acryloyl group, a methacryloyl group, and an oleoyl group.
Q ₂ Is a residue obtained by removing one COOH group from an unsaturated polycarboxylic acid having 4 to 24 carbon atoms or a partial ester-forming derivative thereof, examples of the unsaturated polycarboxylic acid include (anhydrous) maleic acid, fumaric acid, croton Examples include acids, itaconic acid, citraconic acid and the like. Partial ester-forming derivatives are esters, acid anhydrides and acid halides of the above unsaturated polycarboxylic acids having at least one carboxyl group, such as monoalkyl maleate (1 to 12 carbon atoms) ester, monoalkyl fumarate. (C1-C12) ester, Itaconic acid monoalkyl (C1-C12) ester, Citraconic acid monoalkyl (C1-C12) ester is mentioned.
Among X, preferred are an acryloyl group and a methacryloyl group.
[0012]
The number m of hydroxyl groups in the general formula (1) is usually an integer of 2 to 9, preferably 2 to 4. In order to introduce an ethylenically unsaturated bond into (A), rm needs to be 1 to 8, preferably 1 to 4, more preferably 1 or 2, and particularly preferably 2.
When m is 0 or 1, sufficient strength cannot be imparted to the polymer electrolyte. When m exceeds 9, the polymer electrolyte becomes brittle and is liable to cause cracking or chipping. On the other hand, when rm is 0, the polymer electrolyte is not sufficiently cross-linked and the strength tends to be insufficient, and when it exceeds 4, the polymer electrolyte becomes brittle and is liable to cause cracking and chipping.
[0013]
Specific examples of (a) include the following.
(I) the above trivalent alcohol having 3 to 20 carbon atoms and the unsaturated alcohol having 2 to 24 carbon atoms (vinyl alcohol, allyl alcohol, isopropenyl alcohol, oleyl alcohol, etc.) or its AO (as described above) adduct (For example, jumping with methylene bromide, dibromoethane, dibromopropane, dibromobutane, ethylene diiodide, etc.).
[0014]
(Ii) the above trivalent alcohol having 3 to 20 carbon atoms and an unsaturated carboxylic acid having 3 to 25 carbon atoms (acrylic acid, methacrylic acid, oleic acid, etc.), or an unsaturated polycarboxylic acid having 4 to 24 carbon atoms, Partially acylated products by partial esterification reaction with partial ester-forming derivatives thereof (maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester, etc.).
[0015]
(Iii) Partial ether (for example, the above carbon number 1) of the above 4 to 8 carbon number polyhydric alcohol having 5 to 20 carbon atoms and the above unsaturated alcohol having 2 to 24 carbon atoms or the above AO adduct thereof. Obtained by jumping with -4 alkylene dihalides).
[0016]
(Iv) 4-8 valent polyhydric alcohol having 5 to 20 carbon atoms and unsaturated carboxylic acid having 3 to 25 carbon atoms, or unsaturated polycarboxylic acid having 4 to 24 carbon atoms or a portion thereof Partially acylated product by partial esterification reaction with ester-forming derivative.
[0017]
(V) a partial ether of the trivalent monocyclic phenol and the novolak AOA and the unsaturated alcohol having 2 to 24 carbon atoms or the AO adduct thereof (for example, the alkyl having 1 to 4 carbon atoms described above). Obtained by jumping with Range Halide).
[0018]
(Vi) the trivalent monocyclic phenol and the novolak AOA and the unsaturated carboxylic acid having 3 to 25 carbon atoms, or the unsaturated polycarboxylic acid having 4 to 24 carbon atoms or a partial ester-forming derivative thereof. Partially acylated product by partial esterification reaction with
[0019]
Preferred as (a) is a polyol compound in which X is a (meth) acryloyl group in the general formula (1).
As a specific example, the part by partial esterification reaction of said C3-C20 trihydric alcohol or C5-C20 4-10 polyhydric alcohol, and (meth) acrylic acid or its ester formation derivative. It is a (meth) acryloylated product.
[0020]
Specific examples include glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, and sorbitol tetra (meth) acrylate. Moreover, these things can be used individually or in mixture of 2 or more types.
The number average molecular weight of (a) is preferably 130 to 2000, more preferably 140 to 1500 from the viewpoint of the mechanical strength of the polymer electrolyte.
[0021]
(B) is not particularly limited as long as the hydroxyl equivalent is a polyol having a hydroxyl equivalent of 200 to 5000 (valence number 2 to 4 and 5 or more). “Polyurethane Resin Handbook” (Keiji Iwata, September 1987) Polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polybutadiene polyols and the like described on pages 25 to 117, 25th, published by Nikkan Kogyo Shimbun). Among them, polyether polyol is preferable. Examples of polyether polyols include EO adducts of the following low molecular active hydrogen-containing compounds (b-1) to (b-3) and / or co-adducts (random or block) of EO and other AOs.
[0022]
As low molecular active hydrogen-containing compounds,
(B-1) Low molecular polyols: C2-C20 dihydric alcohols (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol , Alkylene glycols such as neopentyl glycol; and alicyclic diols such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trihydric alcohols having 3 to 20 carbon atoms [exemplified in the description of the general formula (1) And 4 to 8 valent polyhydric alcohols having 5 to 20 carbon atoms [as exemplified in the description of the general formula (1)].
(B-2) Polyhydric phenols: monocyclic phenols such as hydroquinone, resorcin, catechol, pyrogallol and phloroglucin; bisphenols such as bisphenol A, bisphenol B, bisphenol F and bisphenol S; and a condensate of phenol and formaldehyde (Novolac); for example, polyphenol described in US Pat. No. 3,265,641.
(B-3) Low molecular amines: ammonia; aliphatic amines having 2 to 20 carbon atoms such as alkanolamines (for example, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine), having 1 to 20 carbon atoms Alkylamines (for example, n-butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), polyalkylenepolyamines having 4 to 20 carbon atoms (carbon of alkylene group) Dialkylenetriamine to hexaalkyleneheptamine having 2 to 6 carbon atoms, such as diethylenetriamine and triethylenetetramine; and aromatic mono- or polyamines having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, Lylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine), alicyclic amines having 4 to 20 carbon atoms (isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine), heterocyclic rings having 4 to 20 carbon atoms Formula amines such as piperazine and aminoethylpiperazine.
[0023]
More preferable as (b) is an EO adduct of the above low molecular polyols and the above polyhydric phenols and / or a coadduct of EO and other AO (random or block).
Particularly preferred are aliphatic diols [as exemplified in the above (b-1)] and aliphatic polyols [as exemplified in the description of the above general formula (1)] and aliphatic triols [in the above general formula (1). EO adducts and / or co-adducts of EO and other AO (random or block) as exemplified in the description, and electrolytes using these are excellent in flexibility and ion conductivity. preferable.
[0024]
The hydroxyl equivalent of (b) is preferably from 200 to 5,000, more preferably from 250 to 3,000, particularly preferably from 300 to 2,000. The hydroxyl equivalent is preferably 250 or more from the viewpoint of mechanical properties of the polymer electrolyte, and preferably 5000 or less from the viewpoint of curability and shape retention of the polymer electrolyte. The amount of EO used in the AO adduct is preferably 5% by mass or more, more preferably 15% by mass or more, and particularly preferably 25% by mass or more in the total mass of AO used for addition. In addition, when using 2 or more types of (b), it is preferable that the weighted average EO content falls in the above range.
[0025]
(C) is an aliphatic polyisocyanate having 2 to 18 carbon atoms (excluding carbon in the isocyanate group, the same shall apply hereinafter), such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2, 2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, etc .; fat having 8 to 15 carbon atoms Cyclic polyisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated T) I), bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate, etc .; aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms such as xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) And the like, and modified products of these polyisocyanates (modified products containing carbodiimide groups, uretdione groups, uretoimine groups, urea groups, burette groups, isocyanurate groups, etc.).
[0026]
Of these, from the viewpoint of chemical resistance and weather resistance, preferred are aliphatic or alicyclic polyisocyanates, more preferred are aliphatic or alicyclic diisocyanates, and particularly preferred are HDI, IPDI and Hydrogenated MDI.
[0027]
In (c), the isocyanate group amount is 2.0 equivalents or less, preferably 1.0 to 1.8 equivalents, more preferably 1 with respect to 1.0 equivalents of active hydrogen in the above (a) and (b). 0.0 to 1.5 equivalents are used. (A) is 1.0 mol% or more with respect to said (b), Preferably it is 2.0 mol%-50 mol%, More preferably, it is 2.5 mol%-25 mol%.
[0028]
(D) is a monomer having an ethylenically unsaturated bond, and includes the following. Moreover, these things can be used individually or in mixture of 2 or more types.
(D-1) Vinyl hydrocarbon (C2-20); aliphatic vinyl hydrocarbon such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, other α-olefins, etc .; alicyclic vinyl hydrocarbons such as cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinyl Cyclohexene, ethylidenebicycloheptene, etc .; aromatic vinyl hydrocarbons such as styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzyls Tylene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, trivinylbenzene, etc.
(D-2) Hydroxyl group-containing vinyl monomers (having 2 to 20 carbon atoms) such as hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxy Ethyl propenyl ether, sucrose allyl ether, etc.
(D-3) Nitrogen-containing vinyl monomers (2 to 20 carbon atoms); amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N- Aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, etc. Amide group-containing vinyl monomers such as (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N ′ Methylene - bis (meth) acrylamide, cinnamic acid amide, N, N- dimethylacrylamide, N, N- dibenzyl acrylamide, methacrylamide formamide, N- methyl-N- vinylacetamide, N- vinyl pyrrolidone.
(D-4) Epoxy group-containing vinyl monomers (having 2 to 20 carbon atoms) such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.
(D-5) Halogen-containing vinyl monomers (having 2 to 20 carbon atoms) such as vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, dichlorostyrene, chloroprene, etc.
(D-6) Vinyl esters, vinyl ethers, vinyl ketones (all having 2 to 20 carbon atoms) such as vinyl formate, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate , Vinyl acylate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, Vinyl 2-butoxyethyl ether, 3,4-dihydro 1,2-pyran, 2-butoxy-2′-vinyloxy diethyl ether, vinyl 2-ethyl mercaptoethyl Ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, dimethyl fumarate, dimethyl maleate, poly ( (Meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane and the like] and the like.
(D-7) alkyl (meth) acrylate (alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.
(D-8) Mono (meth) acrylates of polyalkylene glycols such as (meth) acrylic acid esters having a polyalkylene glycol chain, such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, EO-modified bisphenol A type di (meth) acrylate, and PO modified bisphenol A type di (meth) acrylate. Alkoxyl ethylene glycol (meth) acrylates such as methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate. Alkoxypropylene glycol (meth) acrylates such as ethoxypolypropylene glycol (meth) acrylate, butoxypolypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate and the like.
(D-9) Poly (meth) acrylates of polyhydric (2 to 8 valent) alcohols such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate and the like.
(D-10) Other vinyl monomers (having 2 to 30 carbon atoms) such as acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, cyclohexyl methacrylate, benzyl methacrylate, ethyl α-ethoxy acrylate, phenyl (meth) acrylate, isocyan Natoethyl (meth) acrylate, cyanoacrylate, m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate and the like.
[0029]
Preferred as (d) are the above (d-7), (d-8) and (d-9), and particularly (meth) acrylic acid ester (d1) represented by the following general formula (2). is there.
{CH ₂ = C (R ² ) COO (R ^Three 0) _y −} _z R ^Four (2)
Where R ² Is hydrogen or methyl group, R ^Three Is-(CH ₂ ) ₂ -, -CH (CH _Three ) CH ₂ -, And -CH ₂ CH (CH _Three )-Represents at least one selected from the group-, y represents an integer of 0 or 1 to 40, and z represents an integer of 1 to 8. R ^Four Is a residue obtained by removing all OH groups from a z-valent monool or polyol having a molecular weight of 90 or more and less than 500.
[0030]
As the compound represented by the general formula (2), the following are preferable.
Moreover, these things can be used individually or in mixture of 2 or more types.
[0031]
(D1-1) (meth) acrylic acid ester having a polyalkylene glycol chain, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, EO-modified bisphenol A type di (meth) acrylate, propylene oxide-modified bisphenol Di (meth) acrylate of polyalkylene glycol such as A-type di (meth) acrylate. Alkoxyl ethylene glycol (meth) acrylates such as methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate. Alkoxypropylene glycol (meth) acrylates such as ethoxypolypropylene glycol (meth) acrylate, butoxypolypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate and the like.
[0032]
(D1-2) Poly (meth) acrylates of polyvalent (2-8 valent) alcohols, for example, those mentioned in the above (d-9).
[0033]
Of these, particularly preferred are alkoxy polyethylene glycol (meth) acrylates such as methoxytriethylene glycol (meth) acrylate and ethoxydiethylene glycol acrylate, and trimethylolpropane tri (meth) acrylate.
[0034]
(A1) is obtained by polymerizing (a), (b), (c) and, if necessary, (d), preferably by copolymerizing (a), (b), (c) and (d). More preferably, (a), (b), (c) and (d1) are copolymerized.
[0035]
(A1) is obtained by the urethanization reaction according to (a), (b) and (c) and the reaction of the ethylenically unsaturated bond of (a) and (d) if necessary.
About the manufacturing method of (A1), if it is the method of making (a), (b), (c) and (d) react as needed, it will not specifically limit, A well-known method is employ | adopted.
[0036]
For example, (1) A method in which (a) the unsaturated bond of (d) is reacted if necessary after the urethanization reaction of (a), (b) and (c). (2) A method in which the urethanization reaction of (a), (b), (c) and (a) the unsaturated bond reaction of (d) if necessary proceed simultaneously. (3) (a) After the reaction of the unsaturated bond of (d) if necessary, a method of performing the urethanization reaction of (a), (b), (c) can be mentioned.
[0037]
As a method for performing the urethanization reaction of (1) and (3), for example, (1-i) (b), (c) is reacted, and urethane isocyanate intermediate containing one or more isocyanate groups per molecule A method of reacting the intermediate with (a) after forming the body, (1-ii) urethane isocyanate intermediate containing one or more isocyanate groups per molecule by reacting (a) and (c) (1-iii) a method in which the three components (a), (b), and (c) are reacted together, and the like.
[0038]
In the urethanization reaction, a crosslinking agent and / or an extender can be used as necessary. As the crosslinking agent and / or extender, water can be used in addition to the polyhydric alcohols and polyhydric amines described in pages 122 to 123 of the above-mentioned “Polyurethane resin handbook”. Of these, polyhydric alcohols such as ethylene glycol are preferred.
In the urethanization reaction, the reaction temperature is preferably 50 to 150 ° C.
In this reaction system, a catalyst can be used in order to shorten the reaction time or lower the heating temperature. Examples of the catalyst include tertiary amines (such as triethylamine, triethanolamine, and triethylenediamine) and organic tin compounds (such as dibutyltin laurate and dibutyltin diacetate).
[0039]
The reaction of the ethylenically unsaturated bond is not particularly limited and can be performed by a known method. For example, a method of directly irradiating radiation such as electron beam or γ-ray without adding an initiator, a method of irradiating ultraviolet rays by adding an ultraviolet polymerization initiator such as a photosensitizer, thermal polymerization of an organic peroxide or the like Examples thereof include a method of heating by adding an initiator, and a redox system room temperature reaction using a redox initiator. In particular, the method using ultraviolet irradiation is preferably used because it can be reacted at a low temperature and the reaction time is short, and the method using heating does not require a special apparatus and is simple.
[0040]
Further, the simultaneous advancement of the urethanization reaction and ethylenic unsaturation described in (2) above may be performed by adding the thermal polymerization initiator or heating, or while performing the urethanization reaction by heating, This is achieved by irradiating with ultraviolet rays.
[0041]
Examples of the ultraviolet polymerization initiator include the following.
(A) Benzoin ether polymerization initiator
Benzoin alkyl ether, etc.
(B) Benzophenone polymerization initiator:
Benzophenone, benzyl, methyl orthobenzoylbenzoate, etc.
(C) Acetophenone-based polymerization initiator
Benzyldimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, etc.
(D) Thioxanthone polymerization initiator
2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and the like.
Of these, benzoin ether polymerization initiators are preferred.
Moreover, the usage-amount of a sensitizer is 0.01 to 10 weight% with respect to the whole (A1), Preferably it is 0.05 to 6%, More preferably, it is 0.1 to 4%.
[0042]
The following are mentioned as said thermal-polymerization initiator.
(I) Peroxide polymerization initiator
Acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, 3,5,5- Trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexa Noate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxymaleic acid Tert-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane, t-butyl peroxyacetate, t-butyl peroxy Oxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butylcumyl peroxide, t-butyl hydroperoxide, Di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide De, etc.
[0043]
(Ii) Azo polymerization initiator:
2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis -2,4-dimethylvaleronitrile, etc.
[0044]
Of these, hydroperoxide or peroxyester is preferred, and more specifically, di (4-t-butyl) cyclohexyl peroxydicarbonate or cumene hydroperoxide is preferred.
The usage-amount of a polymerization initiator is 0.1-10 weight% with respect to the whole (A1), Preferably it is 0.1-6%, More preferably, it is 1-4%.
[0045]
In the polymer electrolyte of the present invention, the proportions of the components (a), (b) and (c) are (a), (b) and (c) in that the mechanical strength of the polymer electrolyte is sufficient. ) Is preferably in the following range based on the total weight.
(A) 0.2 to 20% by weight
(B) 50 to 95% by weight
(C) 5 to 50% by weight
[0046]
Moreover, (d) used as needed is 0 to 90 weight% in (A1), Preferably, it is 0 to 75 weight%. Such a ratio of 90% by weight or less is preferable because the mechanical strength of the polymer electrolyte is sufficient.
[0047]
(A) can be a mixture of (A1) and another polymer. The polymer to be mixed is not particularly limited. For example, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), vinyl resin (polyacrylonitrile, polybutadiene, poly (meth) acrylic acid esters, polystyrene, etc.), silicon-containing resin (polyethylene oxide, etc.) Siloxane, polysilane), fluororesin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), and polyphosphazenes.
[0048]
The content of (A1) in (A) is 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more.
[0049]
As (B) used for this invention, what melt | dissolved electrolyte salt (B1) in the nonaqueous solvent (B2) is mentioned. (B1) is not particularly limited as long as it is used for a normal nonaqueous electrolytic solution. Examples of such materials include alkali metal salts, quaternary ammonium salts, amidinium salts, alkaline earth metal salts, and the like. These electrolyte salts can be used alone or as a mixture in use.
[0050]
Examples of the alkali metal salt include lithium salt, sodium salt, and potassium salt. For example, (i) lithium salt includes lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium bistetrafluoroethylenesulfonylimide, lithium Lithium salts such as tristrifluoromethanesulfonylmethide, lithium acetate, lithium trifluoroacetate, lithium benzoate, lithium p-toluenesulfonate, lithium nitrate, lithium bromide, lithium iodide, lithium 4-phenylborate; (ii) sodium Examples of the salt include sodium perchlorate, sodium iodide, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bromide, etc .; (iii) potassium The potassium iodide, potassium tetrafluoride borate, potassium hexafluoride phosphate, potassium salts such as potassium trifluoromethanesulfonate acid.
[0051]
The quaternary ammonium salts include tetramethylammonium / tetrafluoroborate, tetraethylammonium / tetrafluoroborate, tetrapropylammonium / tetrafluoroborate, tetrabutylammonium / tetrafluoroborate, methyl Triethylammonium / 4-fluoroborate, tetraethylammonium / 6-fluorophosphate, tetraethylammonium / perchlorate, or the like, or pyridine ring, pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, pyrimidine ring, 1,5 -Quaternary ammonium salts having a cyclic or bicyclic structure such as diazabicyclo [4,3,0] nonene-5 (DBN) and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) can give.
[0052]
Examples of amidinium salts include 1-ethyl-3-methylimidazolium / 4-fluoroborate, 1,3-dimethylimidazolium / 6-fluorophosphate, 1,3-dimethyl-1,4,5,6. -Tetrahydropyrimidinium / perchlorate and the like.
[0053]
Examples of alkaline earth metal salts include magnesium salts and calcium salts. For example, (i) Mg (ClO _Four ) ₂ , Mg (BF _Four ) ₂ (Ii) Ca (ClO) _Four ) ₂ , Ca (BF _Four ) ₂ And calcium salts.
[0054]
Among these electrolytes, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide and lithium tristrifluoromethanesulfonylmethide exhibit particularly high ionic conductivity and excellent thermal stability. Therefore, it is preferable.
[0055]
Examples of the non-aqueous solvent (B2) include carbonate solvents (propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate), amide solvents (N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N-methylacetamide, N-ethylacetamide, N-methylpyrrolidinone), lactone solvent (γ-butyllactone, γ-valerolactone, 5-valerolactone, 3-methyl-1,3oxazolidine-2-one, etc.) , Alcohol solvent (ethylene glycol, propylene glycol, glycerin, methyl cellosolve, 1,2 butanediol, 1,3 butanediol, 1,4 butanediol, diglycerin, polyoxyalkylene glycol cyclohexanediol , Xylene glycol, etc.), ether solvent (methylal, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane, alkoxypolyalkylene ether, etc.), nitrile solvent (benzonitrile, acetonitrile) , 3-methoxypropionitrile, etc.), phosphoric acids and phosphoric ester solvents (regular phosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, trimethyl phosphate, etc.), 2-imidazolidinones (1,3-dimethyl- 2-imidazolidinone, etc.), pyrrolidones, sulfolane solvents (sulfolane, tetramethylene sulfolane), furan solvents (tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran), dioxolane, dioxane, dichloroethane alone or in combination of these two Less than The solvent mixture can be used. Of these, preferred are carbonate solvents, ether solvents, and furan solvents.
[0056]
The concentration of (B1) in (B) is preferably in the range of 0.25 to 3 mol / liter, particularly preferably 0.5 to 2.5 mol / liter, from the viewpoint of ionic conductivity. .
[0057]
As a method for producing a gel polymer electrolyte, (i) in the absence of (B), (a), (b), (c) and, if necessary, (d) are polymerized and then impregnated with (B) And (ii) a method of polymerizing (a), (b), (c) and, if necessary, (d) in the presence of (B).
[0058]
In (i), (a), (b), (c) and, if necessary, (d) synthesized by a known method are polymerized in the presence of a solvent, and the solvent used is vacuumed if necessary. (A1) is obtained by removing by drying. Next, (A1) is impregnated with (B).
The impregnation of (B) into (A1) is usually performed by immersing (A1) in (B) for 1 to 24 hours in a temperature range of 20 to 80 ° C.
[0059]
The method for polymerizing (A1) in both (i) and (ii) is as described above.
The ratio of (A) and (B) to be used is preferably (A) / (B) = 1/99 to 70/30% by weight. From the viewpoint of mechanical strength, (A) is preferably 1% by weight or more, and preferably 70% by weight or less from the viewpoint of ionic conductivity.
[0060]
Since the gel polymer electrolyte of the present invention exhibits high ionic conductivity, it is suitable as an electrolytic element for an electrolytic capacitor, an electric double layer capacitor, a battery, or an electrochemical device.
[0061]
The gel polymer electrolyte of the present invention uses (a), (b), (c) by using a polyol compound (a) having at least two hydroxyl groups and at least one ethylenically unsaturated bond at the same time. ) And, if necessary, the polyurethane compound comprising (d) has an unsaturated double bond in the branch portion of the molecular chain, and the crosslinking density of the polymer (A1) can be increased. For this reason, it has higher mechanical strength than conventional ones, and can be used with a reduced thickness especially when used in a secondary battery.
[0062]
The secondary battery of the present invention uses a gel polymer electrolyte having the above composition together with a positive electrode and a negative electrode. Generally, a battery is composed of a positive electrode made of a positive electrode active material, a negative electrode made of a negative electrode active material, a diaphragm, and an electrolyte. When the gel polymer electrolyte of the present invention is applied to a battery, the gel polymer electrolyte of the present invention itself can also function as a diaphragm. In addition, when a partition is used, it is easy to integrate the diaphragm with the gel polymer electrolyte of the present invention. The gel polymer electrolyte is directly formed in the battery container having the diaphragm, or the gel is formed in the diaphragm. It can be achieved by impregnating the composition for forming a polymer electrolyte and conducting a polymerization reaction. As the partition walls, those having low resistance to ion migration of the electrolyte solution and excellent in solution retention are used, for example, polyester, polytetrafluoroethylene, polypropylene, polyethylene, polyvinyl alcohol, ethylene-vinyl acetate. Non-woven fabrics or woven fabrics selected from one or more materials such as saponified products of the copolymer are exemplified. These are unnecessary when the gel polymer electrolyte of the present invention itself has a function as a separator.
[0063]
The positive electrode of the battery using the polymer electrolyte of the present invention has (I) LiCoO as its active material. ₂ , LiNiO ₂ , Li _x Ni _y Co _1-y O ₂ (Wherein x and y vary depending on the charge / discharge state of the battery, and usually 0 <x <1, 0.7 <y <1.02), LiMnO ₂ , LiMn ₂ O _Four A composite oxide of lithium and one or more transition metals such as (II) MnO ₂ , V ₂ O _Five Transition metal oxides such as: (III) MoS ₂ TiS ₂ Transition metal sulfides such as (IV) conductive polymers such as polyaniline, polypyrrole, polyacene, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole; A compound that polymerizes can be used. Among these, a composite oxide of lithium and a transition metal is preferable in terms of improving battery capacity and excellent energy density.
[0064]
In forming a positive electrode using such a positive electrode active material, a known conductive agent or binder can be added and used in combination.
[0065]
The negative electrode of a battery using the polymer electrolyte of the present invention uses light metal or light metal ions as its active material. Examples of such light metals include lithium, sodium, potassium, cesium, and aluminum. Similarly, examples of light metal ions include lithium ions, sodium ions, potassium ions, cesium ions, and aluminum ions. Among these, lithium and lithium ions are particularly preferable from the viewpoint of battery output and energy density.
[0066]
The negative electrode is made of the negative electrode active material itself or a material that can occlude and release the active material. As a constituent material of such a negative electrode, (I) a light metal itself; (II) a compound itself having light metal ions; (III) an alloy itself containing these light metals may be used, or (IV) A light metal or a material capable of inserting and extracting ions thereof may be used.
[0067]
Among the constituent materials of such a negative electrode, for example, (IV) as a material capable of occluding and releasing lithium or its ions, for example, (1) graphites, organic polymer compound fired bodies (phenol resin, furan resin, etc.) Carbonaceous materials such as those calcined and carbonized at an appropriate temperature), cokes (pitch coke, needle coke, petroleum coke, etc.), carbon fibers, glassy carbons, pyrolytic carbons, activated carbon, etc .; (2) lithium Polymers such as polyacetylene and polypyrrole which show conductivity by occluding ions can be used. Moreover, as a light metal alloy of (III), a lithium-aluminum alloy etc. can be used, for example.
[0068]
Among these (I) to (IV), it is preferable to use the carbonaceous material (1) of (IV) as a constituent material of the negative electrode from the viewpoint of improving charge / discharge characteristics and self-discharge characteristics. In forming the negative electrode from such a material, a known fixing agent or the like can be added.
[0069]
The shape, form and the like of the battery using the gel polymer electrolyte of the present invention are not particularly limited, and can be arbitrarily selected within the scope of the present invention, such as a coin, a sheet, and a cylinder.
[0070]
The lithium secondary battery of the present invention uses a gel polymer electrolyte having the above composition together with a positive electrode and a negative electrode. A composite oxide of lithium and a transition metal is used for the positive electrode of the battery. Lithium and lithium ions are used as the active material of the negative electrode, and lithium or a material capable of inserting and extracting lithium is used as the constituent material.
[0071]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In the following, parts and% indicate parts by weight and% by weight, respectively. In addition, the nonaqueous solvent and the electrolyte salt were sufficiently purified, and those having a water content of 20 ppm or less and further deoxygenated and denitrogenated were used, and all experimental operations were performed in an argon gas atmosphere. . The ionic conductivity of the gel polymer electrolyte was measured and the strength of the polymer electrolyte was evaluated according to the following method.
[0072]
<Measurement of ion conductivity> An alternating current impedance in which an electrochemical cell is formed by sandwiching a gel polymer electrolyte between stainless steel cylindrical electrodes at 25 ° C., and an alternating current is applied between the electrodes to measure a resistance component. Calculated from the real impedance intercept of the Cole-Cole plot.
[0073]
<Evaluation of compressive breaking strength> Measure the compressive breaking strength of the polymer electrolyte using a creep meter (Yamaden Co., Ltd. RE-3305, plunger diameter 3 mm, sample stage moving speed 0.05 mm / min). It was evaluated by.
[0074]
Example 1
LiBF in a non-aqueous solvent in which propylene carbonate and 1,2-dimethoxyethane were mixed at a volume ratio of 7: 3 _Four Was dissolved in 800.00 parts of electrolyte solution to 3 mol / L, sorbitol diacrylate; 0.66 parts, polyethylene glycol (number average molecular weight 2000); 90.71 parts, HDI; 8.38 parts and dibutyltin 0.10 parts and ethoxydiethylene glycol acrylate; 99.75 parts, benzoin isopropyl ether as a photo radical initiator; 0.40 parts uniformly dissolved, and a gel polymer electrolyte forming composition (C-1) Obtained. After putting the composition for gel-like polymer electrolyte formation (C-1) between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and heating it at 80 ° C. for 3 hours for urethanization reaction The photopolymerization was performed by applying light for 30 minutes with a high-pressure halogen lamp. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 3.5 × 10 ^-3 S / cm, and the compression fracture strength was measured to be 1.5 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0075]
Example 2
800.00 parts of the electrolytic solution used in Example 1 were mixed with sorbitol diacrylate; 0.17 parts, and polyethylene glycol used in Example 1; 45.65 parts, HDI; 4.03 parts and dibutyltin laurate; 0.05 parts and ethoxydiethylene glycol acrylate; 143.53 parts, trimethylolpropane triacrylate; 5.98 parts, benzoyl peroxide as a thermal polymerization initiator; 0.60 parts are uniformly dissolved to form a gel polymer electrolyte A composition (C-2) was obtained. A gel polymer electrolyte forming composition (C-2) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and polymerized by heating at 80 ° C. for 12 hours. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 3.3 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.4 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0076]
Example 3
LiPF in a non-aqueous solvent in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 5: 5 ₆ Electrolyte dissolved in 1 mol / L; 800.00 parts, sorbitol diacrylate; 2.45 parts and EO (50%) / PO (50%) adduct of glycerin (Sanyo Chemical Industries, Ltd.) New Paul GEP-2800, number average molecular weight 2600); 175.67 parts, HDI; 21.28 parts and dibutyltin laurate; 0.2 parts are uniformly dissolved to form a gel polymer electrolyte composition ( C-3) was obtained. After putting the composition for gel polymer electrolyte formation (C-3) between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and heating it at 80 ° C. for 1 hour for urethanization reaction The photopolymerization was performed by applying light for 30 minutes with a high-pressure halogen lamp. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 4.1 × 10. ^-3 S / cm, and the compression breaking strength was measured to find 2.8 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0077]
Example 4
Electrolyte used in Example 3; 800.00 parts, sorbitol diacrylate; 4.51 parts and New Paul GEP-2800 used in Example 3, 161.87 parts, HDI; 25.15 parts and dibutyltin Laurate; 0.19 parts and diethylene glycol monoacrylate; 8.07 parts, benzoin isopropyl ether; 0.20 parts were uniformly dissolved to obtain a gel-like polymer electrolyte forming composition (C-4). A gel-like polymer electrolyte forming composition (C-4) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by applying light for 10 minutes with a high-pressure halogen lamp. Then, it was heated at 80 ° C. for 6 hours to obtain a gel polymer electrolyte. The ionic conductivity of this product is 5.4 × 10 ^-3 S / cm, and the compression fracture strength was measured to be 1.7 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0078]
Example 5
Methoxytriethylene glycol acrylate; 494.70 parts, sorbitol diacrylate; 20.60 parts and polyethylene glycol (PEG-600 number average molecular weight 600); 340.98 parts, HDI; 143.21 parts and dibutyltin laurate; 0.50 part was dissolved, charged into a reaction vessel, and urethanized at 80 ° C. with stirring while blowing dry air. Three hours later, the disappearance of isocyanate was confirmed by the results of IR measurement, and the reaction was terminated. Thus, a mixture (D-1) of a polyurethane compound and methoxytriethylene glycol acrylate was obtained. The resulting mixture (D-1) was a high viscosity liquid. In the electrolyte solution used in Example 3, 800.00 parts, (D-1); 197.61 parts and trimethylolpropane triacrylate; 2.00 parts, benzoin isopropyl ether; 0.40 parts were uniformly dissolved. A composition for forming a gel polymer electrolyte (C-5) was obtained. A gel-like polymer electrolyte forming composition (C-5) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by applying light for 30 minutes with a high-pressure halogen lamp. . When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 5.5 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.6 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0079]
Example 6
10.67 parts of sorbitol diacrylate; polyethylene glycol used in Example 1; 883.22 parts; HDI; 105.10 parts and dibutyltin laurate; 1.0 part were charged into a reaction vessel and stirred at 80 ° C. The urethanization reaction was performed. Three hours later, the disappearance of isocyanate was confirmed by the results of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-6). Electrolytic solution used in Example 1; 800.00 parts (A1-6); 99.85 parts, methoxytriethylene glycol acrylate; 95.76 parts, trimethylolpropane triacrylate; 3.99 parts, benzoin isopropyl ether 0.40 part was melt | dissolved and the composition (C-6) for gel-like polymer electrolyte formation was obtained. A gel-like polymer electrolyte forming composition (C-6) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by irradiating with a high-pressure halogen lamp for 30 minutes. . When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 3.1 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.8 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0080]
Example 7
Methyl ethyl ketone; 800.00 parts pentaerythritol diacrylate; 0.51 parts and Newpol GEP-2800 used in Example 3; 43.37 parts, HDI; 5.96 parts, dibutyltin laurate; 0.05 parts , Ethoxydiethylene glycol acrylate; 148.02 parts, trimethylolpropane triacrylate; 1.50 parts and benzoin isopropyl ether; 0.60 parts were dissolved to obtain a gel-like polymer electrolyte forming composition (C-7). . A composition (C-7) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, photopolymerized by irradiating with a high-pressure halogen lamp for 30 minutes, and then at 80 ° C. for 6 hours. Heated to cause urethanization reaction. The obtained sheet-like polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 for 24 hours at room temperature. Impregnated. Excess electrolyte solution was removed by adsorbing with filter paper to obtain a gel polymer electrolyte. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 2.7 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.8 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0081]
Example 8
Methyl ethyl ketone; 800.00 parts pentaerythritol diacrylate; 0.54 parts polyethylene glycol used in Example 1; 44.11 parts, HDI; 5.19 parts, dibutyltin laurate; 0.05 parts, ethoxydiethylene glycol acrylate 143.53 parts, 5.98 parts of trimethylolpropane triacrylate and 0.60 parts of benzoin isopropyl ether were dissolved to obtain a composition for forming a gel polymer electrolyte (C-8). A composition (C-8) is placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, heated at 80 ° C. for 1 hour, urethanated, and then subjected to a high-pressure halogen lamp for 30 minutes. Photopolymerization was performed by applying light. The obtained sheet-like polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 3 for 24 hours at room temperature. Impregnated. Excess electrolyte solution was removed by adsorbing with filter paper to obtain a gel polymer electrolyte. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 5.2 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.8 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength. .
[0082]
Example 9
Methyl ethyl ketone; 800.00 parts sorbitol diacrylate; 0.14 parts and Newpol GEP-2800 used in Example 3; 53.41 parts, HDI; 6.02 parts, dibutyltin laurate 0.06 parts, diethylene glycol Acrylate; 0.25 parts, ethoxydiethylene glycol acrylate; 136.78 parts, trimethylolpropane triacrylate; 2.79 parts, 0.56 parts of benzoyl peroxide are uniformly dissolved to form a gel polymer electrolyte composition (C -9) was obtained. A gel-like polymer electrolyte forming composition (C-9) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and polymerized by heating at 80 ° C. for 12 hours. The obtained sheet-like polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 for 24 hours at room temperature. Impregnated. Excess electrolyte solution was removed by adsorbing with filter paper to obtain a gel polymer electrolyte. When the ionic conductivity of the gel polymer electrolyte was measured, 3.1 × 10 ^-3 S / cm, and the compression fracture strength was measured to be 1.4 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0083]
Example 10
800.00 parts of the electrolytic solution used in Example 3 were mixed with sorbitol diacrylate; 4.22 parts and New Paul GEP-2800 used in Example 3; 151.21 parts, hydrogenated MDI; 36.65 parts and dibutyl. Tin laurate; 0.19 parts and diethylene glycol monoacrylate; 7.54 parts, benzoin isopropyl ether; 0.20 parts were uniformly dissolved to obtain a gel polymer electrolyte forming composition (C-10). A gel polymer electrolyte forming composition (C-10) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and the temperature was adjusted to 80 ° C. while applying light with a high-pressure halogen lamp. . Light irradiation was completed for 30 minutes and heating was completed in 3 hours to obtain a gel polymer electrolyte. The ionic conductivity of this product is 4.3 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.4 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0084]
Example 11
Methyl ethyl ketone; 800.00 parts pentaerythritol diacrylate; 0.48 parts and Newpol GEP-2800 used in Example 3; 40.66 parts, hydrogenated MDI; 8.71 parts, dibutyltin laurate; 05 parts, ethoxydiethylene glycol acrylate; 148.02 parts, trimethylolpropane triacrylate; 1.50 parts and benzoin isopropyl ether; 0.60 parts are dissolved, and a gel polymer electrolyte forming composition (C-11) is dissolved. Obtained. A composition (C-11) was placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, photopolymerized by irradiating with a high-pressure halogen lamp for 30 minutes, and then 80 ° C. × 6 hours. Heated to cause urethanization reaction. The obtained sheet-like polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 for 24 hours at room temperature. Impregnated. Excess electrolyte solution was removed by adsorbing with filter paper to obtain a gel polymer electrolyte. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 2.7 × 10. ^-3 S / cm, and the compression fracture strength was measured to be 1.7 × 10 ⁷ dyn / cm ² And showed a sufficient solid strength.
[0085]
Comparative Example 1
Electrolyte solution used in Example 1; In 800.00 parts, 195.22 parts of methoxytriethylene glycol acrylate, 3.98 parts of trimethylolpropane triacrylate, and 0.80 parts of benzoin isopropyl ether were uniformly dissolved, A composition for forming a molecular electrolyte (C-1 ′) was obtained. A gel-like polymer electrolyte forming composition (C-1 ′) is placed between two glass plates sandwiched by a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by irradiating with a high-pressure halogen lamp for 10 minutes. It was. The ionic conductivity of the obtained gel polymer electrolyte was measured and found to be 1.1 × 10. ^-3 S / cm, and the compressive breaking strength was measured to be 3.0 × 10 ⁶ dyn / cm ² It was easy to tear.
[0086]
Comparative Example 2
2-hydroxyethyl acrylate; 3.91 parts and the polyethylene glycol used in Example 1; 33.75 parts, HDI; 5.67 parts and dibutyltin laurate; Urethane reaction was performed at 80 ° C. Three hours later, the disappearance of isocyanate was confirmed by the results of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-2 ′). The obtained polyurethane compound (A1-2 ′) was a high-viscosity liquid. Electrolyte used in Example 3; 800.00 parts of (A1-2 ′); 43.38 parts and ethoxydiethylene glycol acrylate; 156.00 parts, benzoin isopropyl ether; A composition for forming a polymer electrolyte (C-2 ′) was obtained. A gel-like polymer electrolyte forming composition (C-2 ′) is placed between two glass plates sandwiched by a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by irradiating with a high-pressure halogen lamp for 10 minutes. It was. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 3.5 × 10 ^-3 S / cm, and the compressive breaking strength was measured to be 9.8 × 10 ⁶ dyn / cm ² Thus, sufficient solid strength could not be obtained.
[0087]
Comparative Example 3
Pentaerythritol triacrylate; 8.81 parts and the polyethylene glycol used in Example 1; 29.56 parts, HDI; 4.97 parts and dibutyltin laurate; The urethanization reaction was carried out at ° C. Three hours later, disappearance of isocyanate was confirmed by the results of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-3 ′). The obtained polyurethane compound (A1-3 ′) was a high-viscosity liquid. Electrolyte used in Example 1; 800 parts, (A1-3 ′); 43.38 parts and ethoxydiethylene glycol acrylate; 156.00 parts, benzoin isopropyl ether; A composition for forming a molecular electrolyte (C-3 ′) was obtained. A gel-like polymer electrolyte forming composition (C-3 ′) is placed between two glass plates sandwiched with a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by applying light for 10 minutes with a high-pressure halogen lamp. It was. When the ionic conductivity of the obtained gel polymer electrolyte was measured, it was 1.5 × 10 ^-3 S / cm, and the compression fracture strength was measured to be 1.0 × 10 ⁷ dyn / cm ² Thus, sufficient solid strength could not be obtained.
[0088]
【The invention's effect】
The gel polymer electrolyte of the present invention has higher ionic conductivity and mechanical strength than conventional ones, and when used in electrochemical elements or electrochemical devices such as electrolytic capacitors, electric double layer capacitors, batteries, etc. Thinning, stacking, simplification and weight reduction of packages are possible.
Therefore, when used as an electrolyte for a secondary battery, the secondary battery is thinned, particularly when used for a gel electrolyte of a lithium secondary battery, despite its small size, high voltage, large electric capacity, A thin lithium battery that has flat discharge characteristics and good low-temperature characteristics and can be used in a wide temperature range becomes possible.
Due to the above effects, the gel polymer electrolyte of the present invention is suitable as an electrolytic capacitor, an electric double layer capacitor, an electrochemical element such as a battery, or an electrolyte for an electrochemical device, particularly a secondary battery material. And is suitably used as a gel polymer electrolyte of a lithium secondary battery.

Claims (9)

In the gel polymer electrolyte comprising the matrix polymer (A) and the non-aqueous electrolyte (B), (A) is an ethylenically unsaturated bond-containing polyol (a) represented by the following general formula (1), other Gel-like polymer comprising a polymer (A1) obtained by polymerizing a polyol (b), an organic polyisocyanate (c), and, if necessary, another monomer (d) having an ethylenically unsaturated bond Electrolytes.
(HO) _m R ¹ (OX) _rm (1)
[Wherein, R ¹ is a residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, m is an integer of 2 to 9, and rm is 1 to 8] Is an integer. ] The electrolyte according to claim 1, wherein, in the general formula (1), X is a (meth) acryloyl group. The electrolyte according to claim 1 or 2, wherein (c) is an aliphatic polyisocyanate and / or an alicyclic polyisocyanate. The electrolyte according to any one of claims 1 to 3, wherein (d) is a (meth) acrylic acid ester (d1) represented by the following general formula (2).
{CH ₂ = C (R ² ) COO (R ³⁰ ) _y −} _z R ⁴ (2)
[Wherein R ² is hydrogen or a methyl group, R ³ is at least one selected from the group of — (CH ₂ ) ₂ —, —CH (CH ₃ ) CH ₂ —, and —CH ₂ CH (CH ₃ ) —. Represents a seed, y represents 0 or an integer of 1 to 40, and z represents an integer of 1 to 8. R ⁴ is a residue obtained by removing all OH groups from a z-valent monool or polyol having a molecular weight of 90 or more and less than 500. ] The electrolyte according to any one of claims 1 to 4, wherein (A) is polymerized in the absence of (B) and then (B) is impregnated in (A). The electrolyte according to any one of claims 1 to 4, wherein (A) is polymerized in the presence of (B). The electrochemical element or electrochemical device formed using the electrolyte of Claims 1-6. The secondary battery comprised from a positive electrode, a negative electrode, and the electrolyte in any one of Claims 1-6. The secondary battery according to claim 8, which is a lithium secondary battery.